Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D11/00—Containers having bodies formed by interconnecting or uniting two or more rigid, or substantially rigid, components made wholly or mainly of plastics material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

• the invention relates to the field of two-component polyurethane compositions, more particularly of structural two-component polyurethane adhesives.
• Two-component polyurethane adhesives based on polyols and polyisocyanates have already been known for a long time.
• Two-component polyurethane adhesives have the advantage that, after mixing, they cure rapidly and so are able to accommodate relatively high forces rapidly after just a short time.
• exacting requirements in respect of strengths and adhesive forces are imposed on such adhesives, since adhesives of this kind constitute elements of load-bearing structures.
• High strengths are typically achieved through high degrees of crosslinking. This is typically achieved through the use of relatively highly polyfunctional polyols or polyamines and relatively highly polyfunctional polyisocyanates.
• EP 1 253 159 A1 discloses in the examples a structural adhesive whose polyol component comprises a mixture of a tetrafunctional aliphatic polyol and a difunctional aliphatic polyol and whose isocyanate component is a prepolymer based on polypropylene glycol and 4,4′-diphenylmethane diisocyanate.
• composition of the invention leads to improved impact toughness of the cured material.
• composition of the invention as a result in particular of the use of an alkoxylated aromatic diol, has improved adhesion to metallic surfaces.
• compositions of the invention are distinguished by outstanding aging stability, more particularly with respect to moisture and temperature fluctuation.
• the present invention relates to a two-component polyurethane composition composed of a polyol component K1 and a polyisocyanate component K2.
• This polyol component K1 comprises at least one alkoxylated aromatic diol A1 and at least one aliphatic triol A2.
• the polyisocyanate component K2 comprises at least one polyisocyanate B1.
• poly in designations such as “polyol”, “polyisocyanate”, “polyether” or “polyamine” indicates in the present document that the substance in question contains, formally, more than one of the functional groups occurring in its name, per molecule.
• aromatic diol here and below is a diol which contains at least one aromatic nucleus and two hydroxyl groups. In the diol there may also be two or more aromatic nuclei present. Preferably the hydroxyl groups are not phenolic groups, i.e., they are advantageously not located directly on the aromatic nucleus.
• the aromatic nucleus may also be fused and/or heteroaromatic and/or a nucleus containing further substituents.
• a heteroaromatic nucleus there are heteroatoms present which are part of the aromatic ring or ring system.
• aromatic nuclei of this kind are substituted benzene, naphthalene, anthracene, phenanthrene, imidazole, pyridine, pyrrole, pyrimidine, pyrazine, quinoline and phenazine.
• diols having two or more aromatic nuclei are diols having the parent structure of a biphenyl, terphenyl, 2,2′-bipyridine, diphenylmethane, 1,1-diphenylethane or 2,2-diphenylpropane.
• Aromatic diols which have shown themselves to be particularly suitable are those prepared from phenol and from formaldehyde, acetaldehyde or acetone or mixtures thereof, more particularly bisphenol A, bisphenol F or bisphenol A/F.
• the alkoxylated aromatic diol A1 is an ethoxylated and/or propoxylated aromatic diol.
• Alkoxylated diols of this kind preferably have the structure of the formula (I)
• the substituent R 1 is a group CH 2 , (CH(CH 3 ) or C(CH 3 ) 2 .
• the segments a 1 and a 1′ denote an oxypropylene unit (PO) and a 2 and a 2′ an oxyethylene unit (EO).
• the dashed lines in formula (I) represent the fact, schematically, that the sequence of the mutually attached alkylene glycol segments a 1 , a 1′ , a 2 and a 2′ is variable. For instance, a blockwise or alternating or random sequence of these oxyalkylene units is possible. Alkoxylated aromatic diols of this kind are prepared in a manner which is known to the skilled worker.
• the two-component polyurethane composition also to contain mixtures of different aromatic diols A1.
• the aromatic diol A1 is used preferably in an amount of 2% to 10% by weight, based on the overall composition.
• the aliphatic triol A2 is an aliphatic triol having a molecular weight of 360 to 6000 g/mol, corresponding to an OH equivalent weight of 120 to 2000, in particular a molecular weight of 120 to 2000 g/mol, preferably of 160 to 1700 g/mol.
• triols there are different kinds of such aliphatic triols.
• they may contain urethane and/or urea and/or ether groups.
• the morphology of the triols may be very different.
• star-shaped or comb-shaped triols are possible.
• the triol it is additionally possible for the triol to contain not only primary but also secondary hydroxyl groups. Preferably all three hydroxyl groups are primary hydroxyl groups.
• Aliphatic triols A2 can be attained, for example, from an aliphatic triisocyanate, more particularly from an isocyanurate, which is formed from three isocyanate molecules, in an excess of aliphatic diols, more particularly of polyetherdiols, where appropriate by further subsequent extension by means of aliphatic diisocyanates and aliphatic diols.
• exemplary aliphatic triols A2 may be obtained from low molecular weight aliphatic triols, such as trimethylolpropane or glycerol, for example, and an aliphatic diisocyanate, with subsequent reaction with an aliphatic diol.
• exemplary aliphatic triols A2 are products of an alkoxylation reaction of low molecular weight aliphatic triols, such as trimethylolpropane or glycerol, for example.
• low molecular weight aliphatic triols such as trimethylolpropane or glycerol, for example.
• these are ethoxylated, or propoxylated or butoxylated, aliphatic triols, more particularly those of trimethylolpropane or glycerol.
• the two-component polyurethane composition also to contain mixtures of different aliphatic triols A2.
• the weight ratio A1/A2 of aromatic diol A1 to aliphatic triol A2 is preferably between 0.05 and 0.3.
• the polyol component K1 may further comprise other constituents. It is advantageous to use curing catalysts. Catalysts of this kind are known to the skilled worker for the reaction of polyisocyanates with polyols, and where appropriate also for reaction with polyamines or water. Examples that may be mentioned of such catalysts include organometallic catalysts of tin, zinc and bismuth, such as dibutyltin dilaurate, or tertiary amines, such as 1,4-diazobicyclo[2.2.2]octane (DABCO), for example.
• DABCO 1,4-diazobicyclo[2.2.2]octane
• diols more particularly polyoxyalkylene-diols, and/or diamines.
• Suitable amines include, in particular, aliphatic, araliphatic, cycloaliphatic and toxicologically unobjectionable aromatic amines.
• the polyisocyanate component K2 comprises at least one polyisocyanate B1.
• polyisocyanate B1 Particularly suitable as polyisocyanate B1 are, on the one hand, polyisocyanates B1′ which in addition to two or more free isocyanate groups contain at least one urea or urethane or biuret or urethdione group. Particularly suitable are polyisocyanates based on aromatic polyisocyanates, more particularly on diphenylmethane diisocyanate (2,4′- and/or 4,4′-MDI). On the one hand, polyisocyanates of the type as available commercially in the form of Desmodur® VH 20 from Bayer have been found particularly suitable. Further suitable polyisocyanates B1 are isocyanurates or biurets of a diisocyanate, more particularly of HDI and/or IPDI and/or TDI.
• polyisocyanates B1′ It is entirely possible to use mixtures of polyisocyanates B1′.
• One preferred embodiment employs a polyisocyanate B1′ mixture of the Desmodur® VH 20 type with an HDI isocyanurate.
• polyisocyanate B1 is particularly suitable as polyisocyanate B1 on the other hand are polyurethane prepolymers B1′′ which contain at least two isocyanate groups and which are formed from a reaction of at least one polyisocyanate having a molecular weight of less than 300 g/mol, more particularly of between 150 g/mol and 270 g/mol, with at least one polyol AB1.
• polyol AB1 are polyols which are selected from the group encompassing polyetherpolyols, polyesterpolyols, polycarbonatepolyols, polyols formed from unsaturated monomers and mixtures thereof.
• polyisocyanates used for this purpose include, in particular, 2,4- and 2,6-tolylene diisocyanate (TDI), 2,4′- and 4,4′-diphenyl-methane diisocyanate (MDI), 1,6-hexamethylene diiso-cyanate (HDI) and the isomer mixtures thereof, and mixtures with one another. MDI is particularly preferred.
• Polyetherpolyols also called polyoxyalkylenepolyols, are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof; where appropriate they are polymerized with the aid of a starter molecule having two or more active hydrogen atoms, such as water, ammonia, or compounds having two or more OH or NH groups, for example, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecan
• polyoxyalkylenepolyols which have a low degree of unsaturation (measured in accordance with ASTM D-2849-69 and reported in milliequivalents of unsaturation per gram of polyol (meq/g)), prepared for example by means of double metal cyanide complex catalysts (DMC catalysts), but also polyoxyalkylenepolyols having a higher degree of unsaturation, prepared for example by means of anionic catalysts such as NaOH, KOH or alkali metal alkoxides.
• DMC catalysts double metal cyanide complex catalysts
• polyoxyalkylenediols or polyoxyalkylenetriols are particularly suitable.
• Acclaim types of specific suitability are polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation of less than 0.02 meq/g and having a molecular weight in the range from 1000 to 30 000 g/mol, and also polyoxypropylenediols and -triols having a molecular weight of 400 to 8000 g/mol.
• molecular weight or “molar weight” is meant, in the present document, always the molecular weight average M n .
• EO-endcapped ethylene oxide-endcapped polyoxypropylene-diols or -triols.
• the latter are special polyoxy-propylene-polyoxyethylenepolyols, obtained for example by alkoxylating pure polyoxypropylenepolyols with ethylene oxide after the end of the polypropoxylation, and which as a result have primary hydroxyl groups.
• Polyesterpolyols are, in particular, polyols which are formed for example from dihydric and/or trihydric alcohols such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexa-hydrophthalic acid or mixtures of the aforementioned acids, and also polyesterpoly
• Particularly preferred polycarbonatepolyols are those obtainable by reacting the abovementioned alcohols—those used to synthesize the polyesterpolyols—with dialkyl carbonates, diaryl carbonates or phosgene.
• polyols formed from unsaturated monomers are meant, in particular, polyols of the kind formed from the polymerization of at least one of the monomers selected from the group encompassing ethylene, propylene, butylene, butadiene, isoprene, styrene, vinyl alcohol, vinyl ethers, vinyl esters, acrylonitrile, acids, amides and esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid and also mixtures thereof.
• Particularly suitable polyols formed from unsaturated monomers are hydroxy-functional polybutadienes such as polybutadienepolyols and hydrogenated polybutadiene-polyols, and also poly(meth)acrylatepolyols.
• (meth)acrylate is meant, here and in the remainder of the present document, esters of both acrylic acid and of methacrylic acid.
• (meth)acrylic acid identifies not only acrylic acid but also methacrylic acid.
• Poly(meth)acrylatepolyols here are polymers which are copolymers of a hydroxy-functional (meth)acrylic ester and at least one further monomer selected from the group encompassing the monomers acrylic acid, methacrylic acid, C 1 -C 18 alkyl esters of acrylic acid or methacrylic acid, styrene, vinyl esters and vinyl alcohol.
• Preferred hydroxy-functional (meth)acrylic esters are hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl(meth)acrylate.
• polyols AB1 preferably have an average molecular weight of 250 to 30 000 g/mol, more particularly of 1000 to 8000 g/mol, and are preferably diols or triols, more particularly having an average OH functionality in the range from 1.6 to 3.
• One preferred embodiment uses a mixture of polyols AB1 which is a mixture of diols and triols.
• the polyisocyanate component K2 comprises at least one polyisocyanate B1′ and at least one polyisocyanate polyurethane prepolymer B1′′.
• Both components K1 and K2 may contain additional constituents in addition to those already mentioned, of the kind the skilled worker knows from two-component polyurethane chemistry. These constituents may be present in only one component or in both. Examples of additional constituents of this kind that are used include solvents, plasticizers and/or extenders, fillers, such as carbon blacks, chalks or talcs, adhesion promoters, more particularly trialkoxysilanes, and thixotropic agents, such as amorphous silicas, and zeolites.
• additional constituents of this kind that are used include solvents, plasticizers and/or extenders, fillers, such as carbon blacks, chalks or talcs, adhesion promoters, more particularly trialkoxysilanes, and thixotropic agents, such as amorphous silicas, and zeolites.
• the components K1 and K2 are advantageously formulated such that the volume ratio of component K1 to component K2 is between 1:3 and 3:1, more particularly between 1:2 and 2:1. With particular preference this ratio is approximately 1:1.
• the mixing ratio is preferably such that the NCO groups of component K2 are stoichiometric in relation to the NCO-reactive groups, typically OH groups, of component K1. If mixing is carried out not with substantial stoichiometry, i.e., with deviations of more than 5%, the reaction of components K1 and K2 is non-optimal, leading to a reduction in the mechanical properties of the cured polyurethane composition. This is true in particular for an excess of the polyol component.
• the components K1 and K2 Prior to application, the components K1 and K2 are stored separately from one another and are mixed with one another only during or immediately prior to application.
• the components are advantageously present in a pack which is composed of two separate chambers, with the polyol component K1 present in one chamber and the polyisocyanate component K2 present in the other chamber.
• the components K1 and K2 are introduced into the chambers of the pack and given an airtight and moisture-tight seal.
• Preferred packages of this kind are, on the one hand, side-by-side double cartridges or coaxial cartridges, in which two tubular chambers are arranged alongside one another or inside one another and are sealed with pistons in an airtight and moisture-tight way.
• the driving of these pistons allows the components to be extruded from the cartridge.
• the ends of the tubes opposite the pistons are modified in such a way, via an adapter where appropriate, that the chamber openings in the region of the opening are connected directly to one another via a dividing wall.
• Packages of this kind are preferred in particular for small-scale applications, in particular for volumes of up to 1 liter.
• the components K1 and K2 are advantageously dispensed and stored in drums or pails.
• the components are extruded via hydraulic presses, in particular by way of follower plates, and are supplied via pipelines to a mixing apparatus of the kind typically used for two-component adhesives in industrial manufacture.
• the polyisocyanate component K2 at least be given an airtight and moisture-tight seal, so that both components can be stored for a long time, i.e., typically longer than 6 months.
• the method of adhesive bonding comprises the following steps:
• Mixing is accomplished typically via static mixers or with the aid of dynamic mixers. At the mixing stage it is important to ensure that the two components are mixed as homogeneously as possible. If the two components are poorly mixed, there are local deviations from the optimum mixing ratio—i.e., substantially stoichiometric—and this has the consequence of an impairment in the mechanical properties of the cured polyurethane composition.
• the two components K1 and K2 have two different colors, which can be distinguished well visually from one another and also from the mixture.
• An example of a color combination of this kind is present when one component is black and the other is white. In that case, effective mixing is present when there is a homogeneous gray color and there are no streaks or patterns in light or dark gray or in white or black.
• the mixed polyurethane composition is applied to at least one substrate surface to be bonded.
• the substrate to be bonded is preferably a metal, plastic, glass or ceramic.
• the partner adherend i.e., the second substrate, to be identical to or different from the first substrate.
• Adhesive may be applied to the first and/or second adherend. Following application of adhesive, the adherends are joined within the open time. Subsequent to joining, the polyurethane composition is cured.
• the polyurethane composition is preferably employed as a structural adhesive. Typical examples of applications for such adhesives are found in built structures, automobiles, vehicles or boats. In these cases the cured adhesive is part of a load-bearing structure and therefore constitutes an important connecting element, whose mechanical properties are subject to exacting requirements. The present invention meets these exacting requirements very well indeed.
• the adhesive composition of the invention exhibits high impact toughness and also an outstanding aging stability, particularly with respect to moisture and temperature fluctuation. Additionally it has been found that the composition of the invention, particularly as a result of the use of an alkoxylated aromatic diol, has an improved adhesion to metallic surfaces.
• the polyol mixture was charged to a vacuum dissolver and, following the addition of catalyst and drying agent, and in the absence of moisture, the mixture was stirred at 25° C. for 20 minutes.
• component K2 dried chalk was added to the polyisocyanate and incorporated homogeneously in a vacuum dissolver, with stirring and under reduced pressure, at 25° C. for 20 minutes. Subsequently this polyisocyanate component K2 was dispensed into the second chamber of the abovementioned side-by-side double cartridge, and was likewise provided with an airtight and moisture-tight seal using a plastic piston.
• Components K1 and K2 were mixed 1:1 volumetrically by means of a static mixer, in the quantities indicated in table 1.
• the mixed components K1 and K2 were introduced into dumbbell molds in accordance with ISO 527, Part 2, 1B and were cured at 25° C. for 24 h and then at 105° C. for 3 h. Following a conditioning time of 24 h at 25° C., elasticity modulus, tensile strength and elongation of the specimens thus produced were measured in accordance with ISO 527 on a Zwick Z020 tensile testing machine, with a test temperature of 20° C. and a test speed of 50 mm/min.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Adhesives Or Adhesive Processes (AREA)

Applications Claiming Priority (4)

Related Parent Applications (1)

Related Child Applications (1)

Publications (2)

Family

ID=34938707

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (1)

Families Citing this family (29)

Citations (7)

Family Cites Families (17)

• 2005
  • 2005-02-11 EP EP20050101001 patent/EP1690880A1/de not_active Withdrawn
• 2006
  • 2006-02-10 WO PCT/EP2006/050853 patent/WO2006084900A2/de active Application Filing
  • 2006-02-10 CN CN2006800099843A patent/CN101151290B/zh active Active
  • 2006-02-10 EP EP06708195.0A patent/EP1851261B2/de active Active
  • 2006-02-10 CA CA002641044A patent/CA2641044A1/en not_active Abandoned
  • 2006-02-10 US US11/884,004 patent/US8790781B2/en not_active Expired - Fee Related
  • 2006-02-10 JP JP2007554566A patent/JP4717082B2/ja active Active
• 2014
  • 2014-03-25 US US14/224,403 patent/US9617033B2/en active Active

Patent Citations (7)

Also Published As

Similar Documents

Legal Events